Note: Descriptions are shown in the official language in which they were submitted.
CA 02584085 2007-04-05
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CA 02584085 2007-04-05
12. An instrument such as any of those described in claims 1; ;but where the
wavelength
selection is achieved using monochromatic sources, su as special lamps, LEDs
or
lasers
13. An instrument such as any of those described in cl ms 1-11, but where the
light source
has been replaced by a continuous (rather than Ised) lamp.
14. An instrument such as any of those describe n claims 1-11, but where an
additional
light source has been added, including las , LED's and continuous lamps
15. Modules having MSL capabilities such those in Claim 1, but provided as an
accessory for laser flash photolysis e ipment, such as, but not limited to,
Luzchem
models LFP-111 and LFP 112.
16. An instrument as described in cla' s 1-14, but where the sample holder or
stage is
separate from the MSL unit and onnected via optical cables and electrical
wires, such
as to provide remote sensing pabilities
17. An instrument such as thos in claims 1-16 where the computer controlling
the
instrumentation is linked b a physical connection, or wireless, of via local
networks or
internet. ;
Background
The product was conceived as an innovation in spectroscopy instrumentation.
The basic
premise is that while a number of spectroscopic measurements are available
individually on the
market, using individual products for each measurement results in duplication
of optics and
other components which could be eliminated by the development of an
integrated, modular
instrument. The concept of a Modular Spectroscopy Laboratory (named MSL) is an
enabling
technology that allows a single expandable hardware platform, a single user
interface, and a
single software package to perform many different spectroscopic measurements.
The MSL is
expandable to incorporate measurements that were not part of an instrument as
initially
constructed and delivered, or even that were developed or invented at a later
time. While
individually each of the measurements currently enabled is available from one
or more
commercial suppliers, and occasionally two measurements are integrated in the
same
instrumeni:, integrating three or more types of measurements using shared
components and
software is a novel technology.
The proposed MSL includes a range of capabilities for at least nine different
types of
measurements where users can choose which combinations suit their needs and
where new
capabilities can be added with a small change to peripheral hardware and
activation of the
related software. Table 1 below summarizes these capabilities, either as
currently developed,
or under development.
The applicant is not aware of any instrument manufacturer that has developed
instrumentation
with the broad capabilities available in MSL products. Thus the key to this
unprecedented
product is not in each capability or in a pair of capabilities, but rather in
the overall range of
three or more user-selected capabiiities that MSL offers in a single platform
and with a common
user interface. Such a wide range of measurement types on a single platform
and with software
capable of using multiple algorithms and controlling a multiplicity of
internal devices, most of
them specific to a given technique, yet making the complexity transparent to
users, is unique.
Most important the MSL is able to make 'intelligent' decisions on a range of
techniques with very
different technical requirements is not available in any current technology.
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To fully coimbine such a broad range of technical capabilities in a manner
that is seamless to the
user requires an integrated software platform managing all capabilities. The
MSL software
controls alll aspects of the hardware and data management such that total
integration of all
available nneasurement is achievable.
This integration operates at three levels:
= MSL-Iab Allows data acquisition, manipulation of instrument devices, and
selection
of capabilities used. i.e., includes hardware interface. Some of the
capabilities that are used in other MSL software modules (e.g. file import
from other instruments) are also available in this module. MSL-lab
includes hardware and software and can operate as a stand-alone
instrument.
= MSL-desk This software product allows data manipulation, including file
import in a
computer that is not connected to MSL hardware. Full data capabilities
excluding data acquisition are available in this product. The product
allows display, overlay, manipulation and calculation of data. This
capability is unique to the MSL, since the norm in spectroscopic
instrumentation is that manipulation is carried out at the instrument, or
exported to general-use programs such as Excel. MSL-desk does not
require hardware beyond the computer and includes full manipulation,
import and export capabilities. MSL-desk in effect enhances the
capabilities of MSL-lab by reducing or eliminating the need to invest
instrument-time to analyze already acquired data. This software function
is essential to the integration of techniques and the unique (multi-)
functionality of the instrument because it allows multi-users or allows
instrument time to be dedicated to data acquisition rather than data
analysis.
= MSL-net This is a server-type application allowing the viewing of MSL data
from
remote computers not having MSL software installed. It has limited
functionality, but only require a web browser. No specialized software
required beyond web browser and internet connectivity are required.
Capabilities include display, overlay and download of spectroscopic data
This software function is essential to the integration of techniques and the
unique (multi-) functionality of the instrument because it allows multi-
users or allows instrument time to be dedicated to data. acquisition rather
than data analysis.
The capabilities of the present invention at present are described in table 1.
Note that:
= The capabilities accessible with the integration concepts of the MSL greatly
exceed
those listed in Table 1, which simply expresses those achievable with hardware
as used
in prototypes.
= Capabilities are not limited to technologies available at present, but can
be expanded to
othier spectroscopic methods that can be invented in the future, provided the
spectral
requirements (e.g., light sources) are already part of MSL's Master Unit, or
can be
added.
= Each of the techniques in Table one by itself does not constitute a new
invention, but
rather, the invention is based on the integration of multiple techniques in a
single
instrument. While some but not all pairs may be commercially available at
present, three
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CA 02584085 2007-04-05
or more techniques in combination are not available. This invention relates to
the
technologies, microcontrollers, positioners, algorithms and software that
through
seamless integration allow multiple measurements to be performed within a
single
platform and user interface.
Table 1: MSL capabilities
Module and function Ca abilit targets
WP2T1 Range: 235 to 850 nm minimum
Spectroradliometer Resolution 1 nm
Wavelength accuracy: 1 nm (against Hg emission lines)
Irradiance reference: Against solar radiation at AM1.5 (ASTM E892 standard).
Can
record maximum solar irradiance at ca. 480 nm (1.5 Wm 2nm-') using no more
than
one third of the detector saturation range (approx. 5000 counts, saturation is
ca.
16,000 counts for USB4000 spectrometer) at integration times of not less than
10
ms.
Dynamic range: minimum 10,000:1
WP2T2 Range: 210 to 850 nm minimum
UV-Vis spectrometer Resolution 1 nm
Wavelength accuracy: 1 nm (against Holmium filter lines)
Sensitivity: minimum 0.002 absorbance units.
Si nal-to-noise: 100:1 on an absorbance of 0.1 at 260 nm
WP3T1 Range: 240 to 850 nm minimum
Diffuse reflectance Resolution 1 nm
spectrometer Wavelength accuracy: 1 nm (against Hg emission lines)
Sensitivity: minimum 0.5 % reflectance change.
Si nal-to-noise: 100:1 on a reflectance of 20% at 300 nm
WP3T2 Spectroscopy:
Stopped flow Range: 230 to 850 nm minimum
Sensitivity: minimum 0.005 absorbance units.
Signal-to-noise: 100:1 on an absorbance change of 0.1 at 400 nm
Resolution 1 nm
Wavelength accuracy: 1 nm (against Holmium filter lines)
Acquisition interval: 20 ms or less
Kinetics:
Mixing time: 2 ms or less
Bandwidth: 2 nm with monochromator (see below)
Time resolution: 2 ms lifetimes to 60 seconds
WP3T3 Emission:
Emission slpectrometer Range: 280 to 850 nm minimum
(also referred as Resolution 1 nm
fluorescence spectrometer) Wavelength accuracy: 1 nm (against Hg emission
lines)
Signal-to-noise: 100:1 on Coumarin-6 emission
Excitation (based on models with linear variable filter):
Range: 230 to 750 nm
Excitation bandwidth: 20 nm (depends on excitation wavelen th
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WP3T3E Excitation (based on models with linear variable filter):
Fluorescence excitation Range: 230 to 750 nm
spectroscopy with the Excitation bandwidth: 20 nm (depends on excitation
wavelength)
Emission spectrometer Data type: 3D data include excitation and emission
simultaneous acquisition
Emission detection:
Range: 280 to 850 nm minimum
Resolution 1 nm
Wavelength accuracy: 1 nm (against Hg emission lines)
Si nal-to-noise: 100:1 on Coumarin-110 emission
WP4T1 Range: 235 to 850 nm minimum
Chemi/bio-luminescence Resolution 1 nm
spectrometer Wavelength accuracy: 1 nm (against Hg emission lines)
Irradiance sensitivity: At least 10-4 weaker against solar radiation at AM1.5
(ASTM
E892 standard). Target sensitivity limit 1 Wm 2nm-1 at 500 nm.
Sensitivity test: Detection of in the luminol system with signal to noise
better than
100:1
WP4T2 Standard:
NIR spectroscopy Range: extension of normal range to 1050 nm in basic models,
up to 1700 nm in
advanced models
Resolution 1 nm with separate spectrometer.
Wavelength accuracy: 1 nm (against Didymium filter lines)
Sensitivity: minimum 0.01 absorbance units.
Signal-to-noise: 100:1 on an absorbance of 0.1 at 900 nm
Extended:
Same as above but with range extended to 1700 nm. This requires a special
detector
WP6 Range: 380 to 850 nm minimum
Thin film metrology Resolution 1 nm
Wavelength accuracy: 1 nm (against Hg emission lines)
Film thickness range: 70 nm to 20 m for films on a reflective or partially
reflective
>2% surface
WP7 Range: 280 to 700 nm minimum (compliant with UPF guidelines)
Ultraviolet protection factor Resolution 1 nm
(UPF) for textile applications Wavelength accuracy: 1 nm (against Hg
emission lines)
Range of UPF values, from 0 to 60 (minimum) covering the range to MAXIMUM
protection.
Note that capabilities WP3T3 and WP3T3E correspond to different experimental
measurements
but utilize the same hardware configuration.
Configuration outline
This invention deals with the development of a miniaturized modular
spectroscopy laboratory
(MSL) consisting of modular instrumentation to perform a variety of
measurements, providing a
consistent and easy user-interface, as well as a seamless file structure that
would permit the
use of common analysis software (kinetic studies, spectral comparisons, global
analysis). Three
main moduies provide the engine to power a variety of spectroscopic
measurements; these
main modules are contained in an instrument box, as required based on the
capabilities that
each instrument may require when delivered, i.e., there is enough flexibility
for some
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CA 02584085 2007-04-05
components not to be included. For example, the wavelength selection
capability may be
needed in some cases. These ideas are shown in graphic form in the following
chart.
Devim and Main modules Devices and
nlessuronments measunntents
LlVatlsible Pulsad xenon Dilluse rMectanea
a'bsorption iamp a tllamant spectroseopy
spectromew lamp
*
Stopped flow
Chsmi- and kinetia
bbluminescence Master unit speewonmftr
sensor CCD spectrometer.
A L flbre optics and
* LabVfEW software gpecvorelometer
~t,a,l , n+~nt met~l~,->'
spectromeDer J
(fluonaeence)
selection niodult lNar IR
61amp roboflcs spOCUDW-OpY
Thin Atm thlcknese Inteqrated In a singM
Instrument booc
The technical concepts that are the subject of this invention apply to many
possible selections of
components. For example in the case of the excitation lamp many continuous and
pulsed lamps
are available. In a one-function instrument, the choice is simple, and either
the best-suited for
the technique or cost-efficiency are the prime considerations. In the case of
the MSL the
selection nequires a balance of the multiple techniques, where the selection
depends more
heavily on the requirements of those techniques that are most challenging. For
example,
fluorescence is more demanding than absorption. In turn, chemiluminescence
requires more
sensitivity than fluorescence. Spectral balance (comparable energy at
different wavelengths) is
more important for absorbance and diffuse reflectance than for other
techniques. Thus the
descriptioris that follow are not exhaustive, but just representative examples
of the possible
components that can be selected for MSL applications. At least all those in
the middle column
have been tested.
Component MSL selection Possible alternatives
Excitation lamp Perkin Elmer 20 Watt Other pulsed lamps, such as those
available from
pulsed xenon lamp Hamamatsu or many continuous lamps, e.g.,
Flashpac model is LS-1 130- Luzchem's xenon illuminator
2 with bulb FX-1 161
Spectrometer Ocean Optics USB4000 Other suppliers including Newport. Further
Ocean
Optics has models such as HR-4000 that will not be
used in basic units, but may be the selection for NIR
and chemi- or bioluminescence applications.
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Start
Collect Dark Yes
Close shutter, Start lamp, Acquire oark
Coilect Sample?
~'' N
y<<
Open shutter. Seiect waveiengtn. Start Iamp, Acqu.re sampie
Display
F Done
~
Data Analysis
This is followed by data analysis and manipulation, as illustrated in the
following flow chart.
Notice that "timed acquisition", also referred as "kinetic acquisition" have
additional hardware
and software requirements. The use of an array detector (CCD miniature
spectrometer) implies
that in all cases of kinetic acquisition the full spectrum (rather than a
single wavelength as in
scanning instruments) is available for each time of acquisition. This array of
data is referred as
"3D" inforrnation.
spectTa
FLUOR, ABS, TFA, DR, Spectrum Overfay
SPR, CLUM, BLUM
Spectrum Math Save Spectrum
Timed Acquisition 3D Pict
Flles
Extract Spectrurn
Extract K netic Trace
EXAMPLES THAT SUPPORT THIS INVENTION
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1) An example of a common combination of techniques:
a) Absorbance
b) Fluorescence
c) Fluorescence excitation
This combination is referred as MSL-FRET (FRET = fluorescence resonance energy
transfer) is
designed for customers who require absorbance, emission (fluorescence) and
fluorescence
excitation as their key instrumental capabilities. 'FRET' instruments can be
expanded to do thin
film thickness, spectroradiometry and diffuse reflectance and all other
techniques common to
MSL products.
MSL-FRET capabilities
This instrument allows the measurement of absorbance (transmission) for liquid
samples
in the 235-850 nm range and of fluorescence (or emission of any kind) in the
300-850
nm range. It allows for both spectroscopic and kinetic measurements.
Its spectral capabilities include absorbance, fluorescence and fluorescence
excitation.
MSL-FRET is unique in that it offers a common, intuitive, user interface for
all
spectroscopic techniques. The data storage techniques of the present invention
allow
for fast easy retrieval and display of thousands of spectra, with intuitive
overlays and
simple spectrum arithmetic functions.
MSL-FRET advantages
MSL instruments invented at Luzchem offer some powerful (and in many cases
unique
advantages). Some key advantages characteristic of MSL-FRET instrumentation
are:
= Price advantage. Since we use many of the same components for absorbance
an emission, we can produce a very cost effective instrument.
= Use of a pulsed lamp reduced dramatically the time the sample is exposed to
light.
= The same user interface and storage modules for all techniques. This reduces
operator training-time and makes spectral overlap (even different techniques)
a
standard feature.
= Measure-now, change-your-mind later. Since the MSL captures CCD data, users
are able to change measurement parameters long after the acquisition has been
completed. For example, if kinetics were monitored at 500 nm at the time of
acquisition, but a few months later it becomes advantageous to display data at
600 nm, the kinetic file can be retrieved and displayed it at any wavelength
within
the monitoring range.
= Measure-now, change-your-mind later. Did you record an excitation spectrum
at
a given emission wavelength, but a different one seems better? No problem,
just
retrieve the kinetic file and display it at any wavelength within the
monitoring
range.
= Need to add a technique such as diffuse reflectance or thin film thickness?
You
can do this easily and in a cost effective manner because key spectroscopic
components are shared.
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= Data structure in spectral lists allows flexible data organization. A given
spectrum can be shared by multiple spectral lists without generating multiple
copies, or can be readily accessed by date, keyword or topic.
= Instrument sharing by multiple users is a key design feature of MSL
products, not
an afterthought. Easy login-logout allows users to return to their spectral
lists.
= User and manager levels within the user interface allow optional control of
delete
functions and new user additions, desirable features for compliant or
educational
applications.
= Reduced energy consumption: Given the current growing environmental
awareness, this type of innovation can contribute to a reduction of negative
environmental impact.
2) Example of the acquisition and display of the absorbance and emission of a
solution
of the common fluorescent dye coumarin-1 10
Sample preparation: samples were prepared by dissolving Coumarin-1 10 (C110
(from Aldrich)
in acetonitrile (Omnisolv, spectroscopy grade). The concentrations of the
obtained solutions
were as follows:
Coumarin-110 1 x 10-5 M and 2 x 10"5 M
The excitation wavelengths for fluorescence was 375 nm for coumarin-1 10. The
samples were
contained in quartz cuvettes, 1.0 cm x 1.0 cm with a Teflon cap on top. The
integration time for
UV and Vis is specified for each file in the "Comments" box in the bottom
right-corner of the
screen shot ( IT = integration time (ms), V = voltage, SAV = samples to
average).
For absorption measurements, the reference was a 1.0 cm x 1.0 cm quartz
cuvette containing
acetonitrile.
The following screen capture illustrates the user interface that allows the
end user to organize
data is spectral lists, whiie the following one shows a display of an
absorbance spectrum for
C110 acquired for a 1 x 10-5 M solution.
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